Compounds of the anthraquinone series



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Patented Oct. 15, 1940 UNITED, STATES OOMPOUNDSOFTHE ANTHRAQUINONE |SERIES No Drawing; ApplicationMarch 25, 1939, Serial No. 2 64,125 j 5 Claims.

This invention relates to the preparation of new compounds of the anthraquinone series. It

relates more particularly to the preparation of new thiophenanthrone carboxylic acid derivatives that are valuable for the synthesis of acidylaminoanthraquinone dyestuffs of modified shades in the yellow to red range and of enhanced'brightness. In U. S 1 P atents 2,049, 214 and1;93l,196 carboxylic "acids of 1:9-thiophenanthrone "are 'de: scribed which are capable of being condensed with aminoanthraquinones'to give'dyestufis that exhibit good dyeing properties. I have found that by-introducing a-ketonic radical on the C- atom of the thiophene ring of 1:9-thiophenanthrone-z-carboxylic acid-.th'at'dyes may be obtained on further condensation with aminoanthraquinones which arenotf only modified in shade but which exhibit'brightness of color not obtainable from the unsubstituted thiophenanthrone carboxylic acids. I r Y I "It" is therefore an object of thi's 'invention to prepare new dyestuff intermediates"-'of 1:9-thiophenanthrone 2-carboiqrlic acid which give dye stufis that .dye -in..bright and desirable shades and which exhibit good dyeing and fastnessi properties. i According to my invention lemercapto 2- anthraquinone carboxylic acid disodium salt. is condensedwith an alpha halogenhetoric of the type in which X stands for halogen, and R stands for a radical of the class consisting of alkyl radicals containing from 1 to 5 carbon atoms and radicals of the benzene series. Ring closure takes place simultaneously with the condensation to give after acidification compounds of the formula OOOH in which R has the same significance as above.

(o1. 2s0--329) v v v This 'carboxylic acid may be f'converted to'the acid chloride by conventional methodssuch as by the use of phosphorus pentachlorideor thionylchloride inorganic solvents. v The following examples are given to illustrate I theinvention. Theparts used are by weight?" Example 1 150 parts of l-chloro-z-anthraquinone car'- boxylic acid are dissolved in a solution of 24 parts sodium hydroxide in 1050. parts water, There is then added a solution of parts sulfur dissolved in 1125 parts of "twenty percent sodium sulfide solution. The mixture is boiled to onehalf the volume, and the resulting mercaptosalt crystallizes out.- This is filtered at room temperature, and then washed with twenty percent salt solution;

Themercaptan cake thus obtained is thensuspended :in 2000.part"s"'water with 40' parts sodium carbonate, and 58.1 parts of chloroacetone are slowly added under agitation.w The violet color soon. disappears and.v after heating. to 150? C., the solution is filtered. from small amounts of. impurity, andthen acidified with, acetic acid. 'Th'e'brightyellow product is filtered, washed with water, and-dried. It dissolves in concentrated sulfuricacid with a bluish-red color, and has the formula 5 I The acid chloride of this compound may be prepared as follows: 24.5- parts of finely ground C- acetyl 1:9 thiophenanthrone-2-carboxylic acid as prepared above are suspended in parts of ortho-dichlorbenzene and 19.3 parts of phosphorous-pentachloride are added. The reaction mass is heated to 110-115 C. for hour. After cooling the greenish yellow product is filtered off and washed with o-dichlorbenzene.

Example 2 partsof l-chloro-2 -anthraquinone carbox ylic acid are converted to the mercaptan as de- P ATEN T OFFICE scribed in Example 1. The mercaptan cake is suspended in 2000 parts of water with 30 parts of sodium carbonate. There is added, with agitation, a solution of 83.? parts omega chloroacetophenone dissolved in 250 parts of alcohol.

The reaction mass is heated to C., filtered from a slight residue, and acidified with acetic acid. The bright yellow product is filtered off, washed with water and dried. The product which gives a red color in concentrated sulfuric acid has the following probable formula II I Example 3 150 parts of l-chloro-Z-anthraquinone carboxylic acid are converted to the mercaptan as described in Example 1, and then suspended in 2000 parts of water.. To this suspension there is added with vigorous agitation 41.3 parts of 1- hloro-Z-butanone. The violet color soon disappears and'the reaction mass is then acidified with parts of acetic acid. The precipitate is filtered off, washed with water and dried. The product is a yellow solid dissolving in concentrated acid with a bluish-red color. It has the formula COOH In the processes above specifically illustrated the corresponding potassium salts, and the alpha bromo ketones may be employed as the starting materials.

I claim:

1. Compounds of the following formula COOH in which R. stands for a substituent of the group consisting of alkyl radicals containing from 1 to 5 carbon atoms and aryl radicals of the benzene I series containing not more than one benzene ring,

said radicals being attached to the carbonyl radical directly thru carbon to carbon linkages. 2. Compounds of the following formula XCO wherein X stands for an alkyl radical containing from 1 to 5 carbon atoms which are attached to the carbonyl radical directly thru carbon to carbon linkages.

3. Compounds of the following formula os ll in which Y stands for an aryl radical of the benzene series which contains not more than 1 benzene ring and which is attached to the carbonyl radical directly thru carbon to carbon linkages.

4. C-acetyl-1,9-thiophenanthrone-2-carboxylic acid.

5. C benzoyl-1,9-thiophenanthrone-2-c.arboxylic acid. I

FREDERIC BENNETT STILMAR. 

